CA1302768C - Photosensitive composition and recording material prepared therewith - Google Patents
Photosensitive composition and recording material prepared therewithInfo
- Publication number
- CA1302768C CA1302768C CA000501207A CA501207A CA1302768C CA 1302768 C CA1302768 C CA 1302768C CA 000501207 A CA000501207 A CA 000501207A CA 501207 A CA501207 A CA 501207A CA 1302768 C CA1302768 C CA 1302768C
- Authority
- CA
- Canada
- Prior art keywords
- photosensitive
- group
- diazonium
- units
- photosensitive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims description 14
- 239000012954 diazonium Substances 0.000 claims abstract description 34
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 238000007639 printing Methods 0.000 claims abstract description 20
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000002252 acyl group Chemical group 0.000 claims abstract description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- -1 alkyl methacrylate Chemical compound 0.000 claims description 14
- 229920001897 terpolymer Polymers 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 3
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical group [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims 2
- 150000003926 acrylamides Chemical class 0.000 claims 1
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 claims 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229940063559 methacrylic acid Drugs 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- ADGJZVKOKVENDN-UHFFFAOYSA-N n-(butoxymethyl)-2-methylprop-2-enamide Chemical compound CCCCOCNC(=O)C(C)=C ADGJZVKOKVENDN-UHFFFAOYSA-N 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229940114077 acrylic acid Drugs 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LXFQSRIDYRFTJW-UHFFFAOYSA-M 2,4,6-trimethylbenzenesulfonate Chemical compound CC1=CC(C)=C(S([O-])(=O)=O)C(C)=C1 LXFQSRIDYRFTJW-UHFFFAOYSA-M 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000005643 Pelargonic acid Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000005521 carbonamide group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- DACIIPAJRAGFMA-UHFFFAOYSA-L 2,5-dimethoxy-4-(4-methylphenyl)sulfanylbenzenediazonium;sulfate Chemical compound [O-]S([O-])(=O)=O.COC1=CC([N+]#N)=C(OC)C=C1SC1=CC=C(C)C=C1.COC1=CC([N+]#N)=C(OC)C=C1SC1=CC=C(C)C=C1 DACIIPAJRAGFMA-UHFFFAOYSA-L 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- ZRDSGWXWQNSQAN-UHFFFAOYSA-N 6-diazo-n-phenylcyclohexa-2,4-dien-1-amine Chemical compound [N-]=[N+]=C1C=CC=CC1NC1=CC=CC=C1 ZRDSGWXWQNSQAN-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000669 Chrome steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000001752 diazonium salt group Chemical group 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 229960004279 formaldehyde Drugs 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940063557 methacrylate Drugs 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YOZHLACIXDCHPV-UHFFFAOYSA-N n-(methoxymethyl)-2-methylprop-2-enamide Chemical compound COCNC(=O)C(C)=C YOZHLACIXDCHPV-UHFFFAOYSA-N 0.000 description 1
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 1
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical class [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000008379 phenol ethers Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/016—Diazonium salts or compounds
- G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
- G03F7/0212—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium compounds
Abstract
ABSTRACT OF THE DISCLOSURE
A photosensitive composition comprising a polymeric diazonium salt, preferably a diazonium salt polycondensation product, and a polymeric binder possessing lateral crosslinking groups represented by the formula -CH2-OR, wherein R denotes a hydrogen atom, a lower alkyl group, a lower acyl group or a lower hydroxyalkyl group, can be used to produce printing plates which yield considerably increased print runs after being baked at temperatures of 150°C to 250°C.
A photosensitive composition comprising a polymeric diazonium salt, preferably a diazonium salt polycondensation product, and a polymeric binder possessing lateral crosslinking groups represented by the formula -CH2-OR, wherein R denotes a hydrogen atom, a lower alkyl group, a lower acyl group or a lower hydroxyalkyl group, can be used to produce printing plates which yield considerably increased print runs after being baked at temperatures of 150°C to 250°C.
Description
13~6~
PHOTOSENSITIVE COMPOSITION AND RECORDING
MATERIAL PREPARED THEREWITH
BACKGROUND OF THE INVENTION
The present invention relates to a negative working photosensitive composition comprising a poly-meric diazonium salt and a polymeric binder, and to a recording material prepared therewith which is par-ticularly suitable for producing lithographic printing plates.
It is known to increase the service life (print run) of an offset printing form by baking, i.e., by heating the printing form to a temperature between about 150 C and 250 C. This process is employed, in particular, for positive working printing plates based on naphthoquinone diazides and, as binders, novolaks or resols (phenol resins), as disclosed by British Patent Specification No. 1,154,749.
Polymeric diazonium salts, particularly diazo-nium salt polycondensation products, have been employed very successfully as photosensitive compounds in nega-tive working printing plates. But it has been almostimpossible heretofore to achieve a substantial increase in print run by baking these plates. In some cases, baking has even led to a decrease in print run, possibly due to a fragmentation of macromolecules in the printing layer.
It has also shown that the phenol resins, and in particular the novolaks, are required as binders in :
3~Z~
positive working layers in order to achieve an optimum increase in print run. These binders are, however, unsuited in practice for use in the above-mentioned negative working layers. It has even been found that photosensitive compositions comprising an excess of phenol resin and diazonium salts which are ~ se nega-tive working turn into positive working compositions (see West German Auslegeschrift No. 20 65 732, Examples 54 and 55).
So that negative working printing plates may nevertheless be baked, it has been proposed to rein-force the developed printing plate with a coating of phenol resin-containing lacquer, which lacquer adheres to the image areas only, and then to bake the plate.
This method is described in British Patent Specification No. 1,151,199. It has not gained general acceptance, however.
European Patent Application No. 0 111 273 describes a photosensitive composition that comprises a binder which is soluble in aqueous-alkaline solutions, a photosensitive substance and, as the crosslinking agent, a melamine derivative. The preferred binders are novolaks. No satisfactory crosslinking is achieved when customary copolymers of (meth)acrylic acid and (meth)acrylic acid esters are used.
French Patent No. 2,485,759 recommends epoxy resins as crosslinking additives to diazo-diphenylamine condensation products. Freshly prepared layers of this kind can be successfully baked, but they have a poor shelf life.
West German Patent Application No. P 33 29 443 describes photopolymerizable compositions comprised of polymerizable, ethylenically unsaturated compounds, photoinitiators and polymeric binders. At least part of the binders employed are polymers having crosslinking lateral groups of the formula -CH2OR, in :
PHOTOSENSITIVE COMPOSITION AND RECORDING
MATERIAL PREPARED THEREWITH
BACKGROUND OF THE INVENTION
The present invention relates to a negative working photosensitive composition comprising a poly-meric diazonium salt and a polymeric binder, and to a recording material prepared therewith which is par-ticularly suitable for producing lithographic printing plates.
It is known to increase the service life (print run) of an offset printing form by baking, i.e., by heating the printing form to a temperature between about 150 C and 250 C. This process is employed, in particular, for positive working printing plates based on naphthoquinone diazides and, as binders, novolaks or resols (phenol resins), as disclosed by British Patent Specification No. 1,154,749.
Polymeric diazonium salts, particularly diazo-nium salt polycondensation products, have been employed very successfully as photosensitive compounds in nega-tive working printing plates. But it has been almostimpossible heretofore to achieve a substantial increase in print run by baking these plates. In some cases, baking has even led to a decrease in print run, possibly due to a fragmentation of macromolecules in the printing layer.
It has also shown that the phenol resins, and in particular the novolaks, are required as binders in :
3~Z~
positive working layers in order to achieve an optimum increase in print run. These binders are, however, unsuited in practice for use in the above-mentioned negative working layers. It has even been found that photosensitive compositions comprising an excess of phenol resin and diazonium salts which are ~ se nega-tive working turn into positive working compositions (see West German Auslegeschrift No. 20 65 732, Examples 54 and 55).
So that negative working printing plates may nevertheless be baked, it has been proposed to rein-force the developed printing plate with a coating of phenol resin-containing lacquer, which lacquer adheres to the image areas only, and then to bake the plate.
This method is described in British Patent Specification No. 1,151,199. It has not gained general acceptance, however.
European Patent Application No. 0 111 273 describes a photosensitive composition that comprises a binder which is soluble in aqueous-alkaline solutions, a photosensitive substance and, as the crosslinking agent, a melamine derivative. The preferred binders are novolaks. No satisfactory crosslinking is achieved when customary copolymers of (meth)acrylic acid and (meth)acrylic acid esters are used.
French Patent No. 2,485,759 recommends epoxy resins as crosslinking additives to diazo-diphenylamine condensation products. Freshly prepared layers of this kind can be successfully baked, but they have a poor shelf life.
West German Patent Application No. P 33 29 443 describes photopolymerizable compositions comprised of polymerizable, ethylenically unsaturated compounds, photoinitiators and polymeric binders. At least part of the binders employed are polymers having crosslinking lateral groups of the formula -CH2OR, in :
.
~.. ~. .. . .
:
' .
--" 13VZ7~B
which R denotes an alkyl group, acyl group or hydroxyalkyl group.
The disclosed compositions are used for the production of thermally curable solder masks.
SUMMARY OF THE PRESENT INVENTION
It is therefore an object of the present inventlon to provide a negative working, thermally curable, photosensitive composition suitable for the production of photosensitive recording material.
It is another object of the present invention to provide a photosensitive recording material which is distinguished by good image resolution, good resistance (i.e.
high print runs following baking), and good storability in the unexposed state.
In accomplishing the foregoing objects, there has been provided, in accordance with one aspect of the present invention a photosensltive composition comprising a polymeric diazonium salt and a polymeric binder, said blnder being a copolymer with compriæes units represented by the formula R' - C - CO NH - CH2 - OR, wherein R denotes a hydrogen atom, a lower alkyl group, a lower acyl group or a lower hydroxyalkyl group and i~
1`~;A
,~
...... .
13~27~i8 R' denotes a hydrogen atom or a methyl group, and units possessing lateral carboxyl groups. In one preferred embodiment, the polymeric diazonium salt is a diazonium salt polycondensation product.
In accordance with another aspect of the present invention, there has been provided a photosensitive recording material comprised of a layer support and a photosensitive layer containing the above-described polymeric binder. Preferably, the recording material is a lithographic printing plate or form.
Other objects, features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the splrit and scope of the lnvention will become apparent to those skilled in the art from thls detailed description.
DETAILED DESCRIPTION OP THE PREPERRED EMBODIMENTS
The present invention is based on a photosensitive composition comprised of a polymeric diazonium salt and a polymeric binder. The mixture of the present invention is characterized by the fact that the binder is a copolymer that comprises units of the formula ~::A .`
3~?Z~6~
' 20731-932 I
R' - C - CO - NH - CH2 - OR, wherein R' denotes a hydrogen atom or a methyl group and R has the above-indicated meaning.
In general, preference is given to compounds wherein R
is an alkyl group. If R is an alkyl group, , ~
' ' ~ - 4a -~ A~
~., ~. ......................... . .
: ' ~ .,;
-- ~L3~Z~8 it generally contains 1 to 6, preferably 1 to 4, carbon atoms; if R is an acyl group, it generally contains l to 4, preferably 1 or 2, carbon atoms.
In addition to the units of the above formula, a suitable copolymer for the present invention may include other units, with preference given to units that yield polymers having a low glass transition temperature (Tg) and that, in particular, contain acry-lic or methacrylic acid ester units.
Upon being heated in the presence of polymers with free hydroxyl groups or, preferably, free carboxyl or carbonamide groups, polymers containing the above-described monomer units yield crosslinked products.
Therefore, they can be present in a mixture with poly-meric binders that carry such substituents. Binders which include both types of functional units in one molecule are preferably employed. Especially suitable are copolymers and, particularly, terpolymers of substituted acrylic or methacrylic acid amides with acrylic or methacrylic acid amide, with acrylic or methacrylic acid, or with alkyl esters oE acrylic or methacrylic acid. Special preference is given to methacrylic acid esters, particularly those containing 4 to 12 carbon atoms in their alkyl groups. If acrylic acid esters are used, the alkyl group can be shorter.
Additionally, the polymers employed in the present invention can contain minor amounts of inter-polymerized hydroxyalkylacrylates or hydroxyalkyl-methacrylates.
The quantitative proportion of carboxyl group-containing units and/or carbonamide-containing units in a copolymer which is suitable for the present invention is determined by the requirement for a trouble-free, rapid development with aqueous, preferably aqueous-alkaline, solutions which are preferably free from organic solvents, and for the highest possible degree _5_ .
;' ~
' ~3~?2~68 of resistance to overdevelopment of the exposed areas.
To a small extent, these properties are also influenced by the mean molecular weight and the chemical and mole-cular nonuniformity of the polymer. In general, the acid number should not exceed 250, and preferably should vary between 50 and 220. In those cases where it is possible to use a developer that contains organic solvents, the acid number can be smaller.
The preferred terpolymers usually contain ~ 10 about 15 to 60% by weight, preferably about 20 to 50%
by weight, of substituted acid amide units. The quan-titative proportion of acrylic or methacrylic acid units is selected in accordance with the above-specified acid numbers; normally, it is about 10 to 35%
by weight. The amount of alkyl acrylate or alkyl methacrylate is within the range of 25 to 75% by weight. Methacrylic acid in its free form or in the form of its alkyl ester is preferred over acrylic acid.
The quantitative proportion of binders in the polymerizable mixture is about 1 to 75% by weight, pre-ferably 5 to 50% by weight, relative to the non-volatile constitutents of the mixture. The binders are preferably prepared by means of a free-radical polymerization in organic solvents, for example, buta-none or ethanol. Optionally, low molecular weight, cross-linkable compounds, such as etherification pro-ducts of hexahydroxymethylmelamine, particularly hexamethoxy-methylmelamine, can be added. The added amount of these compounds can vary between 0.5 and 30%
by weight, in particular up to 20% by weight, relative to the non-volatile constituents of the composition.
Polymeric diazonium salts of the sort employed in the compositions according to the present invention 3S are compounds with recurring, diazonium salt group-containing units. Preference is thereby given to poly-~ !
~3~Z71~3 condensation products of aromatic diazonium salts which are capable of condensation, e.g., diphenylamine-4-dia-zonium salts,with carbonyl compounds capable of conden-sation, e.g., formaldehyde, or methylol compounds capable of condensation, and the ethers and esters thereof. It is also ~ossible to use polymeric diazo-nium salts that are prepared by the polyaddition of diazonium salts or of precursors thereof, as described in European Patent Application No. 0 030 862, or by polymerizing diazonium salts or their precursors, as described in West German Auslegeschrift No. 11 14 704 and West German Offenlegungsschrift No. 33 43 536. The quantitative proportion of polymeric diazonium salt generally varies between 25 and 98% by weight, pre-ferably between 50 and 95% by weight, relative to thenon-volatile constituents of the composition.
Suitable diazonium salt polycondensation pro-ducts are condensation products of aromatic diazonium salts capable of condensation, for example, diphenyl-amine-4-diazonium salts condensed with aldehydes, pre-ferably with formaldehyde. It is particularly advantageous to use cocondensation products containing, in addition to the diazonium salt units, other units which are derived from compounds capable of conden-sation, particularly from aromatic amines, phenols,phenol ethers, aromatic thioethers, aromatic hydrocar-bons, aromatic heterocyclic compounds and organic acid amides. Such condensation products are described in West German Offenlegungsschriften No. 20 24 244 and No.
33 11 435. Generally, all diazonium salt polyconden-sation products described in West German Offenlegungsschrift No. 27 39 774 are suitable.
Diazonium salt units A-N2X used to form the polymeric diazonium salts are preferably derived from compounds corresponding to the formula (Rl-R2-)pR3-N2X, in which ,:, ~3V~7f6~3 X is the anion of the diazonium compound;
p is an integer from 1 to 3;
Rl is an aromatic radical which is capable of condensation, in at least one position, with an active carbonyl compound;
R3 is a substituted or unsubstituted phenylene - group; and R2 is a single bond or one of the following groups:
~(CH2)q~NR4~
--O- (CH2 ) r--NR4--, -S- (CH2 ) r-NR4-, --S--CH2Co-NR4--, -o-R5-O-, -O-, -S-, or --Co-NR4 -, wherein q is a number from 0 to 5, r is a number from 2 to 5, R4 is a hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, an aralkyl group having from 7 to 12 carbon atoms, or an aryl group having from 6 to 12 car-bon atoms, and 25 R5 is an arylene group having from 6 to 12 carbon atoms.
To stabilize the photosensitive composition of the present invention, it is advantageous to add a com-pound which is acid in character. Compounds that can be used include mineral acids and strong organic acids, with phosphoric acid, sulfuric acid, perchloric acid, boric acid and p-toluene sulfonic acid being preferred.
Phosphoric acid is a particularly suitable acid.
Furthermore, other polymeric binders, dyes, pigments~leveling agents, surfactants and other custo-mary additives can be incorporated, in known manner, !
. .
... . .
13~276E~
into compositions according to the present invention.
Compositions oE the present invention are pre-ferably used in the production of photosensitive printing plates, in particular lithographic printing plates. The preferred layer supports in such applica-tions are metals, such as zinc, steel, chromed steel, brass/chromium, copper/chromium or aluminum. For the production of lithographic printing plates, aluminum is preferably employed, in particular mechanically, chemi-cally or electrolytically grained aluminum which is also preferably provided with an oxide layer producedby an anodic process.
Depending on the respective layer consti-tuents, the following substances are examples of suitable solvents for preparing the coating solutions:
alcohols, such as methanol and ethanol; glycol ethers, such as propylene glycol monoethyl ether; dimethyl for-mamide and diethyl formamide; ethers, such as dioxan and tetrahydrofuran; esters, such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate;
ketones, such as methyl ethyl ketone and cyclohexanone.
During processing, the copying material is imagewise exposed through an original. Any light source conventionally used in the copying art that emits radiation in the long-wave ultraviolet range, e.g., carbon arc lamps, mercury high-pressure lamps, pulsed xenon lamps and the like, can be employed for the imagewise exposure. Electron and laser irradiation can also be used for recording images.
After exposure, development is carried out by means of a suitable developer. Aqueous solutions of surfactants, optionally containing an alkali admixture, and mixtures thereof with organic solvents; aqueous salt solutions; aqueous acid solutions, e.g., solutions of phosphoric acids, which, in turn, may contain salts _g _ ,, -` ~3~Z7~8 or organic solvents; and aqueous-alkaline developers, e.g., aqueous solutions of sodium salts of phosphoric acid or silicic acid, can be employed as developers.
Organic solvents may ~lso be added to these developers.
In some cases it is also possible to use organic solvents that have been diluted with water. Further constituents, such as surfactants and hydrophilizing agents, may also be contained in the developers.
Development is performed conventionally, for example, by immersion into and/or by wiping or spraying with developer liquid. Unexposed layer areas are thereby removed.
The following examples illustrate the produc-tion of the photosensitive compositions according to the present invention, and of the recording materials prepared therewith. In the examples, parts by weight (p.b.w.) and parts by volume (p.b.v.) are related to each other as grams and milliliters. Unless otherwise specified, temperatures are indicated in C and percen-tages are expressed in terms of weight.
Example l Coating solutions were prepared from p.b.w. of the polycondensation product obtained from l mol of 3-methoxydiphenylamine-4-diazonium sulfate and l mol of 4,4'-bis-methoxymethyl diphenyl ether, precipi-tated as the mesitylene sulfonate, 1.8 p.b.w. of Victoria Pure Blue FGA (C.I. 42,595) 1 p.b.w. of H3PO4 (85~), and 6 p.b.w. of one of the resinous additives defined below, in 550 p.b.w. of 2-methoxy ethanol and 490 p.b.w. of tetrahydrofuran.
; Each of these solutions was coated onto an electrochemically grained and anodically oxidized alu-;:
.........
~3~Z768 minum plate, which had additionally been treated with a 0.1~ by weight strength solution of polyvinyl phosphonic acid before the coating solution was applied.
The following compounds were employed as addi-tives:
(a) a terpolymer prepared from N-butoxymethyl-methacrylic acid amide, methacrylic acid and hexylmethacrylate (25:25:50), 10 (b) a terpolymer prepared from N-butoxymethyl-methacrylic acid amide, acrylic acid and hexylmethacrylate (47:18:35), (c) a terpolymer prepared from styrene, methacry-lic acid and hexylmethacrylate (10:30:60) (comparison), (d) the bis-glycidyl ether of 2,2-bis(p-hydroxy-phenyl)-propane (comparison).
The presensitized printing plates prepared in this way, which had a layer weight of about 1.5 g/m2 each, were imagewise exposed through a transparent negative original and subsequently developed with the following solution:
2 p.b.w. of Na-dodecylbenzene sulfonate, 1.5 p.b.w. of K2CO3, 1.5 p.b.w. of KHCO3, 1.4 p.b.w. KOH
2 p.b.w. of Graham's salt, 4 p.b.w. of pelargonic acid 2 p.b.w. of poly-N-vinyl-N-methyl-acetamide, 3 p.b.w. of 2-phenoxy-ethanol, and 82.6 p.b.w. of water.
The developed printing plates were cut in two, and one half of each plate was baked at 230 C for 5 minutes.
35The plates were then used for printing in an . .
~: . . , ,-13(~Z7~
offset press. The following numbers of qualit~ prints were obtained.
without_bakinq with_bakinq _ a 100,000 150,000 b 100,000 150,000 c 100,000 110,000 The table shows that the number of prints can be considerably increased by baking when the components according to the present invention are added to the copying layer. Because of the poor storability of the plate containing compound d, this material was not sub-jected to a printing test.
Sections of samples a, b, c and d were stored in a drying cabinet at lOO C for 0.5, 1, 2, 3, and 4 hours, and then exposed through a test original and developed for 1 minute, as described above. Even after storage for 4 hours at lOO C, the quality of printing plates a, b and c did not deteriorate, whereas plate d could not be developed without scum after storage for 30 minutes at 100 C. Unlike samples a, b and c, a sample of plate d could not be developed without scum after a storage time of 4 weeks at room temperature.
Samples of printing plates a and c were exposed through a test original, which comprised a con-tinuous tone step wedge having density increments of0.15 and resolution test elements, by means of a 5 kW
metal halide lamp placed at a distance of 110 cm.
Samples of plates a and c were (1) stored at room temperature for 10 minutes and then developed for 1 minute using the de-veloper described above;
(2) heated to lOO C for 10 minutes and then de-veloped as above; or (3) heated to 120 C for 10 minutes and then de-veloped as above.
I ,~, .
~. .
~L3(:~Z7~3 The number of solid (crosslinked) steps achieved in each case is indicated in the table below:
Treatment Sample a SamPle c__ 10 minutes room temperature 2 2 10 minutes lOO C 4 2 10 minutes 120-C 5 2 The table demonstrates that the photosen-sitivity of the material prepared in accordance with the present invention was increased by a post-heating treatment. Crosslinking of the completely exposed (completely hardened) and partially exposed (partly hardened) areas proceeded faster than in the unexposed areas. No deterioration of image resolution could be observed.
Comparably good results as in above-described Example la were achieved when the polymeric additive employed was (e) a copolymer of N-butoxymethyl-methacrylic acid amide and acrylic acid amide (85:15) or 20 (f) a terpolymer of N-butoxymethyl-methacrylic acid amide, acrylic acid amide and hexylmethacrylate (30:20:50).
ExamPle 2 An aluminum plate, which had been mechanically grained by wire brushing, was coated with a solution of 2 p.b.w. of the polycondensation product obtained from 1 mol of 3-methoxy-diphenylamine-4-diazonium sulfate and 1 mol of form-aldehyde, precipitated as tetrafluoro-borate, 0.15 p.b.w. of Victoria Pure Blue FGA (C.I. 42,595), 0.2 p.b.w. of phosphoric acid (85%) and 1 p.b.w. of one of the polymers described below, :
~ -13-:
' ' ` ` '` ' `
- 13~2768 in p.b.w. of dimethylformamide, 29 p.b.w. of 2-methoxy-ethanol and p.b.w. of tetrahydrofuran and then dried for 2 minutes at llO C.
The following polymers were employed:
(a) a terpolymer prepared from a n-hexylmeth-acrylate, methacrylic acid and N-butoxymethyl-methacrylamide (36:28:36);
10 (b) a terpolymer prepared from n-hexylmethacryl-ate, methacrylic acid and styrene (60:30:10) (comparison).
The plates were exposed, and one half of each plate was then heated to 210-C for 5 minutes.
Thereafter, the resistance of each plate to solvents was tested. For this purpose, the plates were wiped for 1 minute with cotton pads which had been soaked with dimethyl sulfoxide, and were then judged.
not heated heated _ . . .__ _ a strong attack, no substantial layer detached attack b as (a) attack, layer detached Similar results were achieved when the even more aggressive solvent dimethyl formamide was used, i.e., the layer according to the present invention was thermally crosslinkable and was resistant after crosslinking.
When the above diazonium salt polycondensation product was replaced by a polycondensation product which was obtained from 1 mol of 3-methoxy-diphenyl-amine-4-diazonium sulfate and 1 mol of 4,4'-bis-meth-oxymethyl-diphenyl ether, precipitated as the tetrafluoroborate; or was obtained from 0.8 mol of ,~
~3~Z768 2,5-dimethoxy-4-(p-tolylmercapto)-benzene diazonium sulfate, 0.2 mol of diphenylamine-4-diazoni~m sulfate and 1 mol of formaldehyde, precipitated as the tetrafluoroborate, it was also possible to obtain ther-mal crosslinking after the addition of a binderaccording to the present invention. A considerably increased resistance to chemical and chemical/mechan-ical attacks was thus achieved.
Example 3 10An electrochemically grained and anodically oxidized aluminum plate was coated with a solution of 2 p.b.w. of the diazonium salt polycondensation product specified in Example 1, 2 p.b.w. of a terpolymer obtained from N-butoxy-15methyl-methacrylamide, methacrylic acid and ethyl acrylate (31:32:37), 0.2 p.b.w. of Victoria Pure Blue FGA (C.I. 42,595), and 0.1 p.b.w. of phosphoric acid (85%), in p.b.w. of 2-methoxy-ethanol and p.b.w. of tetrahydrofuran A layer weight of 1.2 g/m2 was obtained after drying. The printing plate was exposed through a test original and developed with the developer of Example 1.
Half of the plate was heated to 230 C for 5 minutes.
The heated and the non-heated sample were together mounted on an offset press. In a comparative simultaneous print test, the wear of the partially exposed (partly hardened) steps of a continuous-tone step wedge of the plate which was not a post-heated plate was much greater than was observed in the case of the post-heated plate. The unheated plate became unu-seable after about 110,000 to 120,000 prints, i.e., it produced gray prints of poor contrast, whereas the .
.
13~2~6E3 heated plate still printed images that were reproduced in great detail and showed good ink transfer proper-ties.
Comparable results were achieved using ter-polymers obtained from N-butoxymethyl-methacrylamide, methacrylic acid and decylmethacrylate (23:30:47); and using N-butoxymethyl-methacrylamide, acrylic acid and - hexylmethacrylate (26:22:52).
Example 4 An electrochemically grained and anodically oxidized aluminum plate was coated with a solution of 2 p.b.w. of a cocondensate obtained from 1 mol of 3-methoxy-diphenylamine-4-diazonium sulfate, 1 mol of 4-methoxy-methyl-4'-methyl-diphenyl ether and 1 mol of 4,4'-bis-methoxymethyl-diphenyl ether, precipitated as the mesitylene sulfonate, 0.2 p.b.w. of a terpolymer obtained from styrene, n-hexyl-methacrylate and methacrylic acid (10:60:30, molecular weight 35,000), 0.1 p.b.w. of a copolymer of N-methoxymethyl meth-acrylamide and n-hexylmethacrylate (50:50), 0.2 p.b.w. of hexamethoxymethyl melamine, 0.2 p.b.w. of Victoria Pure Blue FGA (C.I. 42,595) and 0.2 p.b.w. of phosphoric acid (85%), in 55 p.b.w. of 2-methoxy-ethanol and 35 p.b.w. of tetrahydrofuran.
A layer weight of 0.8 g/m2 was obtained. The plate was exposed through a test original and developed with the following solution:
15 p.b.w. of pelargonic acid, 10 p.b.w. of sodium hydroxide, ' 13(~Z~
92 p.b.w. of a block polymer comprising 90% of pro-pylene oxide and 10% of ethylene oxide, and 12 p.b.w. of sodium tetrapolyphosphate, in 550 p.b.w. of water.
The plate was then heated to 210-C for 10 mi-nutes. It yielded very high print runs of excellent quality.
, :~' ' ' . ' ' ' ' ` ' ` ', :
~.. ~. .. . .
:
' .
--" 13VZ7~B
which R denotes an alkyl group, acyl group or hydroxyalkyl group.
The disclosed compositions are used for the production of thermally curable solder masks.
SUMMARY OF THE PRESENT INVENTION
It is therefore an object of the present inventlon to provide a negative working, thermally curable, photosensitive composition suitable for the production of photosensitive recording material.
It is another object of the present invention to provide a photosensitive recording material which is distinguished by good image resolution, good resistance (i.e.
high print runs following baking), and good storability in the unexposed state.
In accomplishing the foregoing objects, there has been provided, in accordance with one aspect of the present invention a photosensltive composition comprising a polymeric diazonium salt and a polymeric binder, said blnder being a copolymer with compriæes units represented by the formula R' - C - CO NH - CH2 - OR, wherein R denotes a hydrogen atom, a lower alkyl group, a lower acyl group or a lower hydroxyalkyl group and i~
1`~;A
,~
...... .
13~27~i8 R' denotes a hydrogen atom or a methyl group, and units possessing lateral carboxyl groups. In one preferred embodiment, the polymeric diazonium salt is a diazonium salt polycondensation product.
In accordance with another aspect of the present invention, there has been provided a photosensitive recording material comprised of a layer support and a photosensitive layer containing the above-described polymeric binder. Preferably, the recording material is a lithographic printing plate or form.
Other objects, features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the splrit and scope of the lnvention will become apparent to those skilled in the art from thls detailed description.
DETAILED DESCRIPTION OP THE PREPERRED EMBODIMENTS
The present invention is based on a photosensitive composition comprised of a polymeric diazonium salt and a polymeric binder. The mixture of the present invention is characterized by the fact that the binder is a copolymer that comprises units of the formula ~::A .`
3~?Z~6~
' 20731-932 I
R' - C - CO - NH - CH2 - OR, wherein R' denotes a hydrogen atom or a methyl group and R has the above-indicated meaning.
In general, preference is given to compounds wherein R
is an alkyl group. If R is an alkyl group, , ~
' ' ~ - 4a -~ A~
~., ~. ......................... . .
: ' ~ .,;
-- ~L3~Z~8 it generally contains 1 to 6, preferably 1 to 4, carbon atoms; if R is an acyl group, it generally contains l to 4, preferably 1 or 2, carbon atoms.
In addition to the units of the above formula, a suitable copolymer for the present invention may include other units, with preference given to units that yield polymers having a low glass transition temperature (Tg) and that, in particular, contain acry-lic or methacrylic acid ester units.
Upon being heated in the presence of polymers with free hydroxyl groups or, preferably, free carboxyl or carbonamide groups, polymers containing the above-described monomer units yield crosslinked products.
Therefore, they can be present in a mixture with poly-meric binders that carry such substituents. Binders which include both types of functional units in one molecule are preferably employed. Especially suitable are copolymers and, particularly, terpolymers of substituted acrylic or methacrylic acid amides with acrylic or methacrylic acid amide, with acrylic or methacrylic acid, or with alkyl esters oE acrylic or methacrylic acid. Special preference is given to methacrylic acid esters, particularly those containing 4 to 12 carbon atoms in their alkyl groups. If acrylic acid esters are used, the alkyl group can be shorter.
Additionally, the polymers employed in the present invention can contain minor amounts of inter-polymerized hydroxyalkylacrylates or hydroxyalkyl-methacrylates.
The quantitative proportion of carboxyl group-containing units and/or carbonamide-containing units in a copolymer which is suitable for the present invention is determined by the requirement for a trouble-free, rapid development with aqueous, preferably aqueous-alkaline, solutions which are preferably free from organic solvents, and for the highest possible degree _5_ .
;' ~
' ~3~?2~68 of resistance to overdevelopment of the exposed areas.
To a small extent, these properties are also influenced by the mean molecular weight and the chemical and mole-cular nonuniformity of the polymer. In general, the acid number should not exceed 250, and preferably should vary between 50 and 220. In those cases where it is possible to use a developer that contains organic solvents, the acid number can be smaller.
The preferred terpolymers usually contain ~ 10 about 15 to 60% by weight, preferably about 20 to 50%
by weight, of substituted acid amide units. The quan-titative proportion of acrylic or methacrylic acid units is selected in accordance with the above-specified acid numbers; normally, it is about 10 to 35%
by weight. The amount of alkyl acrylate or alkyl methacrylate is within the range of 25 to 75% by weight. Methacrylic acid in its free form or in the form of its alkyl ester is preferred over acrylic acid.
The quantitative proportion of binders in the polymerizable mixture is about 1 to 75% by weight, pre-ferably 5 to 50% by weight, relative to the non-volatile constitutents of the mixture. The binders are preferably prepared by means of a free-radical polymerization in organic solvents, for example, buta-none or ethanol. Optionally, low molecular weight, cross-linkable compounds, such as etherification pro-ducts of hexahydroxymethylmelamine, particularly hexamethoxy-methylmelamine, can be added. The added amount of these compounds can vary between 0.5 and 30%
by weight, in particular up to 20% by weight, relative to the non-volatile constituents of the composition.
Polymeric diazonium salts of the sort employed in the compositions according to the present invention 3S are compounds with recurring, diazonium salt group-containing units. Preference is thereby given to poly-~ !
~3~Z71~3 condensation products of aromatic diazonium salts which are capable of condensation, e.g., diphenylamine-4-dia-zonium salts,with carbonyl compounds capable of conden-sation, e.g., formaldehyde, or methylol compounds capable of condensation, and the ethers and esters thereof. It is also ~ossible to use polymeric diazo-nium salts that are prepared by the polyaddition of diazonium salts or of precursors thereof, as described in European Patent Application No. 0 030 862, or by polymerizing diazonium salts or their precursors, as described in West German Auslegeschrift No. 11 14 704 and West German Offenlegungsschrift No. 33 43 536. The quantitative proportion of polymeric diazonium salt generally varies between 25 and 98% by weight, pre-ferably between 50 and 95% by weight, relative to thenon-volatile constituents of the composition.
Suitable diazonium salt polycondensation pro-ducts are condensation products of aromatic diazonium salts capable of condensation, for example, diphenyl-amine-4-diazonium salts condensed with aldehydes, pre-ferably with formaldehyde. It is particularly advantageous to use cocondensation products containing, in addition to the diazonium salt units, other units which are derived from compounds capable of conden-sation, particularly from aromatic amines, phenols,phenol ethers, aromatic thioethers, aromatic hydrocar-bons, aromatic heterocyclic compounds and organic acid amides. Such condensation products are described in West German Offenlegungsschriften No. 20 24 244 and No.
33 11 435. Generally, all diazonium salt polyconden-sation products described in West German Offenlegungsschrift No. 27 39 774 are suitable.
Diazonium salt units A-N2X used to form the polymeric diazonium salts are preferably derived from compounds corresponding to the formula (Rl-R2-)pR3-N2X, in which ,:, ~3V~7f6~3 X is the anion of the diazonium compound;
p is an integer from 1 to 3;
Rl is an aromatic radical which is capable of condensation, in at least one position, with an active carbonyl compound;
R3 is a substituted or unsubstituted phenylene - group; and R2 is a single bond or one of the following groups:
~(CH2)q~NR4~
--O- (CH2 ) r--NR4--, -S- (CH2 ) r-NR4-, --S--CH2Co-NR4--, -o-R5-O-, -O-, -S-, or --Co-NR4 -, wherein q is a number from 0 to 5, r is a number from 2 to 5, R4 is a hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, an aralkyl group having from 7 to 12 carbon atoms, or an aryl group having from 6 to 12 car-bon atoms, and 25 R5 is an arylene group having from 6 to 12 carbon atoms.
To stabilize the photosensitive composition of the present invention, it is advantageous to add a com-pound which is acid in character. Compounds that can be used include mineral acids and strong organic acids, with phosphoric acid, sulfuric acid, perchloric acid, boric acid and p-toluene sulfonic acid being preferred.
Phosphoric acid is a particularly suitable acid.
Furthermore, other polymeric binders, dyes, pigments~leveling agents, surfactants and other custo-mary additives can be incorporated, in known manner, !
. .
... . .
13~276E~
into compositions according to the present invention.
Compositions oE the present invention are pre-ferably used in the production of photosensitive printing plates, in particular lithographic printing plates. The preferred layer supports in such applica-tions are metals, such as zinc, steel, chromed steel, brass/chromium, copper/chromium or aluminum. For the production of lithographic printing plates, aluminum is preferably employed, in particular mechanically, chemi-cally or electrolytically grained aluminum which is also preferably provided with an oxide layer producedby an anodic process.
Depending on the respective layer consti-tuents, the following substances are examples of suitable solvents for preparing the coating solutions:
alcohols, such as methanol and ethanol; glycol ethers, such as propylene glycol monoethyl ether; dimethyl for-mamide and diethyl formamide; ethers, such as dioxan and tetrahydrofuran; esters, such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate;
ketones, such as methyl ethyl ketone and cyclohexanone.
During processing, the copying material is imagewise exposed through an original. Any light source conventionally used in the copying art that emits radiation in the long-wave ultraviolet range, e.g., carbon arc lamps, mercury high-pressure lamps, pulsed xenon lamps and the like, can be employed for the imagewise exposure. Electron and laser irradiation can also be used for recording images.
After exposure, development is carried out by means of a suitable developer. Aqueous solutions of surfactants, optionally containing an alkali admixture, and mixtures thereof with organic solvents; aqueous salt solutions; aqueous acid solutions, e.g., solutions of phosphoric acids, which, in turn, may contain salts _g _ ,, -` ~3~Z7~8 or organic solvents; and aqueous-alkaline developers, e.g., aqueous solutions of sodium salts of phosphoric acid or silicic acid, can be employed as developers.
Organic solvents may ~lso be added to these developers.
In some cases it is also possible to use organic solvents that have been diluted with water. Further constituents, such as surfactants and hydrophilizing agents, may also be contained in the developers.
Development is performed conventionally, for example, by immersion into and/or by wiping or spraying with developer liquid. Unexposed layer areas are thereby removed.
The following examples illustrate the produc-tion of the photosensitive compositions according to the present invention, and of the recording materials prepared therewith. In the examples, parts by weight (p.b.w.) and parts by volume (p.b.v.) are related to each other as grams and milliliters. Unless otherwise specified, temperatures are indicated in C and percen-tages are expressed in terms of weight.
Example l Coating solutions were prepared from p.b.w. of the polycondensation product obtained from l mol of 3-methoxydiphenylamine-4-diazonium sulfate and l mol of 4,4'-bis-methoxymethyl diphenyl ether, precipi-tated as the mesitylene sulfonate, 1.8 p.b.w. of Victoria Pure Blue FGA (C.I. 42,595) 1 p.b.w. of H3PO4 (85~), and 6 p.b.w. of one of the resinous additives defined below, in 550 p.b.w. of 2-methoxy ethanol and 490 p.b.w. of tetrahydrofuran.
; Each of these solutions was coated onto an electrochemically grained and anodically oxidized alu-;:
.........
~3~Z768 minum plate, which had additionally been treated with a 0.1~ by weight strength solution of polyvinyl phosphonic acid before the coating solution was applied.
The following compounds were employed as addi-tives:
(a) a terpolymer prepared from N-butoxymethyl-methacrylic acid amide, methacrylic acid and hexylmethacrylate (25:25:50), 10 (b) a terpolymer prepared from N-butoxymethyl-methacrylic acid amide, acrylic acid and hexylmethacrylate (47:18:35), (c) a terpolymer prepared from styrene, methacry-lic acid and hexylmethacrylate (10:30:60) (comparison), (d) the bis-glycidyl ether of 2,2-bis(p-hydroxy-phenyl)-propane (comparison).
The presensitized printing plates prepared in this way, which had a layer weight of about 1.5 g/m2 each, were imagewise exposed through a transparent negative original and subsequently developed with the following solution:
2 p.b.w. of Na-dodecylbenzene sulfonate, 1.5 p.b.w. of K2CO3, 1.5 p.b.w. of KHCO3, 1.4 p.b.w. KOH
2 p.b.w. of Graham's salt, 4 p.b.w. of pelargonic acid 2 p.b.w. of poly-N-vinyl-N-methyl-acetamide, 3 p.b.w. of 2-phenoxy-ethanol, and 82.6 p.b.w. of water.
The developed printing plates were cut in two, and one half of each plate was baked at 230 C for 5 minutes.
35The plates were then used for printing in an . .
~: . . , ,-13(~Z7~
offset press. The following numbers of qualit~ prints were obtained.
without_bakinq with_bakinq _ a 100,000 150,000 b 100,000 150,000 c 100,000 110,000 The table shows that the number of prints can be considerably increased by baking when the components according to the present invention are added to the copying layer. Because of the poor storability of the plate containing compound d, this material was not sub-jected to a printing test.
Sections of samples a, b, c and d were stored in a drying cabinet at lOO C for 0.5, 1, 2, 3, and 4 hours, and then exposed through a test original and developed for 1 minute, as described above. Even after storage for 4 hours at lOO C, the quality of printing plates a, b and c did not deteriorate, whereas plate d could not be developed without scum after storage for 30 minutes at 100 C. Unlike samples a, b and c, a sample of plate d could not be developed without scum after a storage time of 4 weeks at room temperature.
Samples of printing plates a and c were exposed through a test original, which comprised a con-tinuous tone step wedge having density increments of0.15 and resolution test elements, by means of a 5 kW
metal halide lamp placed at a distance of 110 cm.
Samples of plates a and c were (1) stored at room temperature for 10 minutes and then developed for 1 minute using the de-veloper described above;
(2) heated to lOO C for 10 minutes and then de-veloped as above; or (3) heated to 120 C for 10 minutes and then de-veloped as above.
I ,~, .
~. .
~L3(:~Z7~3 The number of solid (crosslinked) steps achieved in each case is indicated in the table below:
Treatment Sample a SamPle c__ 10 minutes room temperature 2 2 10 minutes lOO C 4 2 10 minutes 120-C 5 2 The table demonstrates that the photosen-sitivity of the material prepared in accordance with the present invention was increased by a post-heating treatment. Crosslinking of the completely exposed (completely hardened) and partially exposed (partly hardened) areas proceeded faster than in the unexposed areas. No deterioration of image resolution could be observed.
Comparably good results as in above-described Example la were achieved when the polymeric additive employed was (e) a copolymer of N-butoxymethyl-methacrylic acid amide and acrylic acid amide (85:15) or 20 (f) a terpolymer of N-butoxymethyl-methacrylic acid amide, acrylic acid amide and hexylmethacrylate (30:20:50).
ExamPle 2 An aluminum plate, which had been mechanically grained by wire brushing, was coated with a solution of 2 p.b.w. of the polycondensation product obtained from 1 mol of 3-methoxy-diphenylamine-4-diazonium sulfate and 1 mol of form-aldehyde, precipitated as tetrafluoro-borate, 0.15 p.b.w. of Victoria Pure Blue FGA (C.I. 42,595), 0.2 p.b.w. of phosphoric acid (85%) and 1 p.b.w. of one of the polymers described below, :
~ -13-:
' ' ` ` '` ' `
- 13~2768 in p.b.w. of dimethylformamide, 29 p.b.w. of 2-methoxy-ethanol and p.b.w. of tetrahydrofuran and then dried for 2 minutes at llO C.
The following polymers were employed:
(a) a terpolymer prepared from a n-hexylmeth-acrylate, methacrylic acid and N-butoxymethyl-methacrylamide (36:28:36);
10 (b) a terpolymer prepared from n-hexylmethacryl-ate, methacrylic acid and styrene (60:30:10) (comparison).
The plates were exposed, and one half of each plate was then heated to 210-C for 5 minutes.
Thereafter, the resistance of each plate to solvents was tested. For this purpose, the plates were wiped for 1 minute with cotton pads which had been soaked with dimethyl sulfoxide, and were then judged.
not heated heated _ . . .__ _ a strong attack, no substantial layer detached attack b as (a) attack, layer detached Similar results were achieved when the even more aggressive solvent dimethyl formamide was used, i.e., the layer according to the present invention was thermally crosslinkable and was resistant after crosslinking.
When the above diazonium salt polycondensation product was replaced by a polycondensation product which was obtained from 1 mol of 3-methoxy-diphenyl-amine-4-diazonium sulfate and 1 mol of 4,4'-bis-meth-oxymethyl-diphenyl ether, precipitated as the tetrafluoroborate; or was obtained from 0.8 mol of ,~
~3~Z768 2,5-dimethoxy-4-(p-tolylmercapto)-benzene diazonium sulfate, 0.2 mol of diphenylamine-4-diazoni~m sulfate and 1 mol of formaldehyde, precipitated as the tetrafluoroborate, it was also possible to obtain ther-mal crosslinking after the addition of a binderaccording to the present invention. A considerably increased resistance to chemical and chemical/mechan-ical attacks was thus achieved.
Example 3 10An electrochemically grained and anodically oxidized aluminum plate was coated with a solution of 2 p.b.w. of the diazonium salt polycondensation product specified in Example 1, 2 p.b.w. of a terpolymer obtained from N-butoxy-15methyl-methacrylamide, methacrylic acid and ethyl acrylate (31:32:37), 0.2 p.b.w. of Victoria Pure Blue FGA (C.I. 42,595), and 0.1 p.b.w. of phosphoric acid (85%), in p.b.w. of 2-methoxy-ethanol and p.b.w. of tetrahydrofuran A layer weight of 1.2 g/m2 was obtained after drying. The printing plate was exposed through a test original and developed with the developer of Example 1.
Half of the plate was heated to 230 C for 5 minutes.
The heated and the non-heated sample were together mounted on an offset press. In a comparative simultaneous print test, the wear of the partially exposed (partly hardened) steps of a continuous-tone step wedge of the plate which was not a post-heated plate was much greater than was observed in the case of the post-heated plate. The unheated plate became unu-seable after about 110,000 to 120,000 prints, i.e., it produced gray prints of poor contrast, whereas the .
.
13~2~6E3 heated plate still printed images that were reproduced in great detail and showed good ink transfer proper-ties.
Comparable results were achieved using ter-polymers obtained from N-butoxymethyl-methacrylamide, methacrylic acid and decylmethacrylate (23:30:47); and using N-butoxymethyl-methacrylamide, acrylic acid and - hexylmethacrylate (26:22:52).
Example 4 An electrochemically grained and anodically oxidized aluminum plate was coated with a solution of 2 p.b.w. of a cocondensate obtained from 1 mol of 3-methoxy-diphenylamine-4-diazonium sulfate, 1 mol of 4-methoxy-methyl-4'-methyl-diphenyl ether and 1 mol of 4,4'-bis-methoxymethyl-diphenyl ether, precipitated as the mesitylene sulfonate, 0.2 p.b.w. of a terpolymer obtained from styrene, n-hexyl-methacrylate and methacrylic acid (10:60:30, molecular weight 35,000), 0.1 p.b.w. of a copolymer of N-methoxymethyl meth-acrylamide and n-hexylmethacrylate (50:50), 0.2 p.b.w. of hexamethoxymethyl melamine, 0.2 p.b.w. of Victoria Pure Blue FGA (C.I. 42,595) and 0.2 p.b.w. of phosphoric acid (85%), in 55 p.b.w. of 2-methoxy-ethanol and 35 p.b.w. of tetrahydrofuran.
A layer weight of 0.8 g/m2 was obtained. The plate was exposed through a test original and developed with the following solution:
15 p.b.w. of pelargonic acid, 10 p.b.w. of sodium hydroxide, ' 13(~Z~
92 p.b.w. of a block polymer comprising 90% of pro-pylene oxide and 10% of ethylene oxide, and 12 p.b.w. of sodium tetrapolyphosphate, in 550 p.b.w. of water.
The plate was then heated to 210-C for 10 mi-nutes. It yielded very high print runs of excellent quality.
, :~' ' ' . ' ' ' ' ` ' ` ', :
Claims (10)
1. A photosensitive composition comprising a polymeric diazonium salt and a polymeric binder, said binder being a copolymer with comprises units represented by the formula wherein R denotes a hydrogen atom, a lower alkyl group, a lower acyl group or a lower hydroxyalkyl group and R' denotes a hydrogen atom or a methyl group, and units possessing lateral carboxyl groups.
2. A photosensitive composition as claimed in Claim 1, wherein the polymeric diazonium salt is a diazonium salt polycondensation product.
3. A photosensitive composition as claimed in Claim 1, wherein said copolymer further comprises units possessing lateral carboxylic acid amide groups.
4. A photosensitive composition as claimed in Claim 1, wherein said copolymer is a terpolymer of (a) methacrylic acid or acrylic acid, (b) an acrylamide or methacrylamide carrying ROCH2-groups at the nitrogen, and (c) an alkyl acrylate or alkyl methacrylate.
5. A photosensitive composition as claimed in Claim 4, wherein said terpolymer comprises 10 to 35% by weight of units derived from acrylic acid or methacrylic acid, 15 to 60% by weight of units derived from substituted acrylamide or substituted methacrylamide, and 25 to 75% by weight of units derived from an alkyl acrylate or alkyl methacrylate.
6. A photosensitive mixture as claimed in Claim 2, wherein the diazonium salt polycondensation product is comprised of recurring units A-N2X and B which are linked by intermediate groups, wherein A is a radical of an aromatic diazonium compound capable of condensation with formaldehyde, and B is a radical of a diazonium group-free compound capable of condensation with formaldehyde.
7. A photosensitive mixture as claimed in Claim 6, wherein said intermediate groups are methylene groups derived from carbonyl compounds capable of condensation.
8. A photosensitive mixture as claimed in Claim 6, wherein the diazonium group-free compound is selected from the group consisting of an aromatic amine, a phenol ether, an aromatic thioether, an aromatic hydrocarbon, an aromatic heterocyclic compound and an organic acid amide.
9. A photosensitive recording material comprised of a layer support and a photosensitive layer, said photosensitive layer comprising a composition according to any one of claims 1 to 8.
10. A photosensitive recording material as claimed in Claim 9, wherein said recording material is a lithographic printing plate.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853504658 DE3504658A1 (en) | 1985-02-12 | 1985-02-12 | LIGHT-SENSITIVE MIXTURE AND RECORDING MATERIAL MADE THEREFOR |
DEP3504658.9 | 1985-02-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1302768C true CA1302768C (en) | 1992-06-09 |
Family
ID=6262235
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000501207A Expired - Fee Related CA1302768C (en) | 1985-02-12 | 1986-02-06 | Photosensitive composition and recording material prepared therewith |
Country Status (7)
Country | Link |
---|---|
US (1) | US4749639A (en) |
EP (1) | EP0191400B1 (en) |
JP (1) | JPS61186956A (en) |
BR (1) | BR8600553A (en) |
CA (1) | CA1302768C (en) |
DE (2) | DE3504658A1 (en) |
FI (1) | FI860589A (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3528929A1 (en) * | 1985-08-13 | 1987-02-26 | Hoechst Ag | RADIATION-SENSITIVE MIXTURE, THIS CONTAINING RADIATION-SENSITIVE RECORDING MATERIAL AND METHOD FOR THE PRODUCTION OF RELIEF IMAGES |
DE3617499A1 (en) * | 1986-05-24 | 1987-11-26 | Hoechst Ag | LIGHT SENSITIVE MIXTURE AND LIGHT SENSITIVE RECORDING MATERIAL MADE THEREOF |
US4914000A (en) * | 1988-02-03 | 1990-04-03 | Hoechst Celanese Corporation | Three dimensional reproduction material diazonium condensates and use in light sensitive |
JP2657516B2 (en) * | 1988-04-05 | 1997-09-24 | コニカ株式会社 | Photosensitive composition |
JP2546403B2 (en) * | 1989-09-14 | 1996-10-23 | 凸版印刷株式会社 | Photosensitive resin composition |
JP2555741B2 (en) * | 1989-09-14 | 1996-11-20 | 凸版印刷株式会社 | Color filter manufacturing method |
US5464538A (en) * | 1989-12-29 | 1995-11-07 | The Dow Chemical Company | Reverse osmosis membrane |
US5310581A (en) * | 1989-12-29 | 1994-05-10 | The Dow Chemical Company | Photocurable compositions |
US5238747A (en) * | 1989-12-29 | 1993-08-24 | The Dow Chemical Company | Photocurable compositions |
JPH03257402A (en) * | 1990-03-07 | 1991-11-15 | Toppan Printing Co Ltd | Production of color filter |
US6017682A (en) * | 1995-03-14 | 2000-01-25 | Internatonal Business Machines Corporation | Solid state extension method |
US6699636B2 (en) | 2001-12-12 | 2004-03-02 | Kodak Polychrome Graphics Llc | Imaging element comprising a thermally activated crosslinking agent |
US8137896B2 (en) * | 2008-07-29 | 2012-03-20 | Eastman Kodak Company | Method of preparing lithographic printing plates |
JP5593405B2 (en) * | 2012-02-28 | 2014-09-24 | 富士フイルム株式会社 | Photosensitive resin composition, method for producing cured film, cured film, organic EL display device and liquid crystal display device |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1447963B2 (en) * | 1965-11-24 | 1972-09-07 | KaIIe AG, 6202 Wiesbaden Biebnch | PROCESS FOR MANUFACTURING AN OFFSET PRINTING FORM FROM A PRESENSITIZED PRINTING PLATE MATERIAL |
GB1235281A (en) * | 1967-02-18 | 1971-06-09 | Howson Algraphy Ltd | Improvements in or relating to lithographic printing plates |
US3679419A (en) * | 1969-05-20 | 1972-07-25 | Azoplate Corp | Light-sensitive diazo condensate containing reproduction material |
BE789196A (en) * | 1971-09-25 | 1973-03-22 | Kalle Ag | PHOTOSENSITIVE COPY MATERIAL |
JPS527364B2 (en) * | 1973-07-23 | 1977-03-02 | ||
DE2834059A1 (en) * | 1978-08-03 | 1980-02-14 | Hoechst Ag | LIGHT SENSITIVE COPY MATERIAL AND METHOD FOR THE PRODUCTION THEREOF |
NL8001085A (en) * | 1979-02-27 | 1980-08-29 | Minnesota Mining & Mfg | PHOTOSENSITIVE MATERIALS AND OBJECTS. |
DE2941960A1 (en) * | 1979-10-17 | 1981-04-30 | Hoechst Ag, 6000 Frankfurt | DEVELOPER MIXTURE AND METHOD FOR DEVELOPING EXPOSED LIGHT-SENSITIVE COPY LAYERS |
US4316949A (en) * | 1979-12-14 | 1982-02-23 | Minnesota Mining And Manufacturing Company | Photoreactive oligomer composition and printing plate |
JPS58137834A (en) * | 1982-02-09 | 1983-08-16 | Kuraray Co Ltd | Photosensitive composition |
DE3329443A1 (en) * | 1983-08-16 | 1985-03-07 | Hoechst Ag, 6230 Frankfurt | POLYMERIZABLE MIXTURE BY RADIATION AND COPY MATERIAL MADE THEREOF |
-
1985
- 1985-02-12 DE DE19853504658 patent/DE3504658A1/en not_active Withdrawn
-
1986
- 1986-02-04 DE DE8686101413T patent/DE3683379D1/en not_active Expired - Fee Related
- 1986-02-04 EP EP86101413A patent/EP0191400B1/en not_active Expired - Lifetime
- 1986-02-06 CA CA000501207A patent/CA1302768C/en not_active Expired - Fee Related
- 1986-02-07 BR BR8600553A patent/BR8600553A/en not_active IP Right Cessation
- 1986-02-07 US US06/827,163 patent/US4749639A/en not_active Expired - Fee Related
- 1986-02-10 FI FI860589A patent/FI860589A/en not_active Application Discontinuation
- 1986-02-12 JP JP61027000A patent/JPS61186956A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
EP0191400B1 (en) | 1992-01-15 |
EP0191400A2 (en) | 1986-08-20 |
BR8600553A (en) | 1986-10-21 |
DE3504658A1 (en) | 1986-08-14 |
DE3683379D1 (en) | 1992-02-27 |
US4749639A (en) | 1988-06-07 |
FI860589A (en) | 1986-08-13 |
EP0191400A3 (en) | 1988-01-13 |
FI860589A0 (en) | 1986-02-10 |
JPS61186956A (en) | 1986-08-20 |
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